EP0077175A2 - Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom - Google Patents
Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom Download PDFInfo
- Publication number
- EP0077175A2 EP0077175A2 EP82305313A EP82305313A EP0077175A2 EP 0077175 A2 EP0077175 A2 EP 0077175A2 EP 82305313 A EP82305313 A EP 82305313A EP 82305313 A EP82305313 A EP 82305313A EP 0077175 A2 EP0077175 A2 EP 0077175A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxazolidone
- acid
- prepolymer
- urethane
- linkages
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 101
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- -1 dicyclohexyl oxide carboxylates Chemical class 0.000 claims description 6
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000010107 reaction injection moulding Methods 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 235000011044 succinic acid Nutrition 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 25
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 18
- 229920005862 polyol Polymers 0.000 description 18
- 150000003077 polyols Chemical class 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 150000002118 epoxides Chemical class 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LBXYOQUOUHELKC-UHFFFAOYSA-O [NH2+]=C=O.O=C1N=[C-]OC1 Chemical class [NH2+]=C=O.O=C1N=[C-]OC1 LBXYOQUOUHELKC-UHFFFAOYSA-O 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical class O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2120/00—Compositions for reaction injection moulding processes
Definitions
- the present invention relates to compositions for the production of poly(oxazolidone/urethane) thermosets and to products prepared therefrom.
- U.S. Patent No. 3,313,747 to C. H. Schramm describes formation of isocyanate-oxazolidone derivatives by reacting a polyisocyanate with a diepoxide to yield a polyisocyanate-2-oxazolidone compound containing at least two 2-oxazolidone groups and two isocyanate groups. These compounds can be reacted with various polymerization or curing agents including polyols. Polymers resulting from reaction using a polyol curing agent would not contain ester linkages since a carboxylic acid reagent is not used in their synthesis.
- U.S. Patent No. 4,066,628 to K. Ashida et al. illustrates preparation of a urethane-modified polyoxazolidone by reacting a diisocyanate and a diepoxide to form an isocyanate-terminated polyoxazolidone which is then reacted with a glycol.
- the resulting polymer composition contains both oxazolidone and urethane linkages in the same polymer chain or backbone of the recurring unit.
- U.S. Patent'No. 4,220,731 to P. Zuppinger relates to formation of crosslinked polymers by reacting a liquid epoxide compound, a polyisocyanate and a polyhydroxy compound, including a polyester polyol, if desired.
- the recurring unit would contain oxazolidone and urethane linkages in the same polymer chain.
- the present invention relates to reaction mixtures comprising a polyisocyanate and an epoxy and hydroxy-group containing prepolymer formed by reaction of a diepoxy compound with a mono- or, preferably, dicarboxylic acid.
- the prepolymer has an equal number of epoxy and hydroxy groups, the hydroxy group or groups being secondary and in a non-terminal position. Reaction of the polyisocyante with such a prepolymer yields a poly(oxazolidone/urethane) thermoset which is substantially free of isocyanurate linkages.
- the oxazolidone rings form in the polymer backbone of the recurring unit in the polymer composition due to reaction of the terminal epoxy groups with isocyanate groups, said oxazolidone groups being separated from one another by ester linkages which are derived from the acid reactant used to make the prepolymer.
- ester linkages which are derived from the acid reactant used to make the prepolymer.
- the reaction mixture which is the subject matter of the present invention comprises a polyisocyanate and a prepolymer containing equal numbers of terminal epoxy groups and secondary, non-terminal hydroxy groups. Reaction of the polyisocyanate with the epoxy group of the prepolymer forms oxazolidone groups; reaction with the non-terminal, secondary hydroxy groups, urethane side chains in the recurring unit.
- any polyisocyanate capable of reaction with the epoxy and hydroxy groups contained in the prepolymer to form the desired oxazolidone and urethane linkages is contemplated for use by the present invention.
- suitable conventional polyisocyanates which are used to form urethane polymers, for example, include such aromatic and aliphatic types as: the tolylene diisocyanates, such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; the methylene bis(phenyl isocyanates), such as methylene bis (4-phenyl isocyanate); dianisidine diisocyanate, toluidine diisocyanate, m-xylene diisocyanate, 1,5-naphthylene diisocyanate, p-phenylene diisocyanate, and hexamethylene diisocyanate and other di- and higher polyisocyanates. Mixtures of such isocyanates can be used, if desired.
- the prepolymer which forms the other major reaction ingredient has the formula where R, R 1 and R 2 are independently any grouping of atoms to which a carbon atom can be covalently linked including, substituted or unsubstituted alkylene, arylene, alkylene-arylene and (for R) hydrogen and x is a positive integer of either 1 or 2.
- R, R 1 and R 2 are independently any grouping of atoms to which a carbon atom can be covalently linked including, substituted or unsubstituted alkylene, arylene, alkylene-arylene and (for R) hydrogen and x is a positive integer of either 1 or 2.
- These prepolymers are formed by reacting a diepoxide with either a monocarboxylic acid or, preferably, a dicarboxylic acid, under conditions such that the prepolymer contains equal molar amounts of reactable epoxy groups and reactable secondary non-terminal hydroxy groups.
- R can be any of the groups described above for R, R 1 or R 2 .
- Reaction of monocarboxylic acids will generally result in a statistical mixture of desired prepolymer, fully reacted epoxide reagent containing no terminal epoxy groups, and unreacted diepoxide. It should be appreciated that the prepolymer resulting from the reaction of a monoacid and the diepoxide has one terminal epoxy group and one secondary hydroxy group. The end of the prepolymer remote from the terminal epoxy group is capped with an ester linkage. Reaction of a diisocyanate, for example, with such a prepolymer produces oxazolidone and urethane linkages in the same chain of the recurring unit, i.e., the polymer backbone, with the ester groups being in pendant side chains.
- Reaction of diacids with the diepoxides is favored and is preferably carried out using slightly more than two moles of diepoxide to diacid. In this manner all the acid is reacted and a prepolymer is formed by reacting the terminal epoxy group of one epoxide reactant with one end of the diacid and the terminal epoxy group of another epoxide reactant with the other end of the diacid:
- the prepolymer that results is preferably, substantially acid free and has one or two terminal epoxy groups, each with an associated, non-terminal secondary hydroxy group.
- the diepoxide and acid reactants that can be used to form the prepolymers described above can be selected from a wide variety of compounds as long as the above type of reaction occurs.
- diepoxides shown in U.S. Patent No. 4,066,628 to K. Ashida et al., which is incorporated herein by reference, can be employed for use in connection with the present invention.
- diepoxides include the diglycidyl ethers of dihydric mononuclear and fused ring phenols, the diglycidyl ethers of non-fused polynuclear phenols having an alkylene, sulfone, carboxy, oxygen or sulfur bridging group between the phenol rings, the diglycidyl ethers of novolac resins, dicyclopentadiene dioxide, vinyl cyclohexane dioxide, the dicyclohexyl oxide carboxylates, and the diglycidyl derivatives of aromatic primary amines.
- Some representative diepoxides include the diglycidyl ethers of bisphenol A, hydroquinone, resorcinal, catechol, methylhydroquinone, 1,6-hexanediol, and 1,12-dodecanediol; alicyclic diepoxides, such as vinylcyclohexene dioxide, and dicyclopentadiene dioxide.
- the acids that can be used include the saturat- edfand unsaturated mono-and dicarboxylic acids.
- the prepolymer is combined with the desired polyisocyanate to form a reaction mixture from which the poly(oxazolidone/ urethane) thermoset compositions can be formed, including those of the present invention which depend upon use of a diacid reactant to form the prepolymer.
- the reaction medium can contain up to about 60%, by weight, of other materials which do not interfere with the reaction of the prepolymer and polyisocyanate. Representative ingredients include additional diepoxide (which can function as a solvent, if liquid), diol, acrylate or methacrylate ester monomer or polymer to impart flexibility to the final product.
- the reaction mixture can contain up to 10%, by weight, of one or more of the following additives: blowing agents, flame retardants, mold releasing agents, dyes, and stabilizers.
- the amount of polyisocyanate chosen for reaction with the prepolymer should be substantially equivalent in regard to its isocyanate functionality (on an equivalent basis) to the total equivalents of epoxide and hydroxy groups in the composition from the prepolymer and any added ingredients which would react with the isocyanate.
- a slight excess of isocyanate (up to about 5% on a weight basis) can be tolerated but greater amounts should be avoided since the formation of isocyananurate linkages would be favored.
- the respective molar amount of oxazolidone and urethane linkages to one another in the thermoset will depend upon the presence of other isocyanate reactive groups added to the reaction mixture.
- oxazolidone:urethane a 50:50 (oxazolidone:urethane) molar ratio polymer is produced.
- Addition of additional hydroxy group compounds, e.g., polyol, will yield a larger molar amount of urethane, whereas addition of epoxide materials, e.g., diepoxides, will increaset h e oxazolidone content of the product.
- the molar amount of oxazolidone to urethane can range from 90:10 to 4:96.
- the reaction mixture of polyisocyanate and prepolymer can also contain a catalytically effective amount (e.g., from about 0.002% to about 2%, based on the weight of all reaction ingredients of an oxazolidone and/or urethane formation catalyst.
- a catalytically effective amount e.g., from about 0.002% to about 2%, based on the weight of all reaction ingredients of an oxazolidone and/or urethane formation catalyst.
- Representative catalysts tending to favor oxazolidone formation include the quarternary ammonium salts (e.g., tetramethyl ammonium chloride); the metal alkoxides (e.g., lithium n-butoxide); the metal halides and their complexes (e.g., lithium chloride/hexamethylphosphor- amide complex); and the organometallic compounds (e.g. trialkyl aluminum).
- Catalysts which favor urethane formation include the organotin compounds, diamines, and polyamines.
- thermoset composition formed from the above-described reaction mixture is one which contains oxazolidone and urethane linkages and which is essentially free of substantial amounts of isocyanurate linkages.
- the oxazolidone linkages are in the polymer backbone of the main recurring unit in virtue of their formation by reaction of.the polyisocyanate with a terminal epoxy group in the prepolymer.
- the urethane groups are in side chains in the main recurring unit of the polymer, rather than in the backbone of the recurring unit which contains the oxazolidone linkages, when a diacid is used to form the prepolymer described herein, in view of their formation by reaction of the polyisocyanate with the pendant, non-terminal hydroxy groups in such a prepolymer.
- Ester groups also lie in the polymer backbone of the unit and separate the oxazolidone groups. These ester groups are derived by reason of the reaction of a carboxylic acid with a diepoxide in forming the prepolymer.
- thermoset compositions of the present invention which are derived from the reaction of the prepolymer and the polyisocyanate, has the formula reproduced below which is bounded by dotted lines:
- R, Ri, R 2 and R 3 in the above formula can be any of the groups described earlier for R, R 1 and R 2 in the prepolymer and can be such groups as alkylene, arylene, and alkylene-arylene groups. Any grouping of atoms to which a carbon atom can be covalently linked can be selected for R-R 3 .
- R 4 -R 15 are the same as R-R 3 and also include hydrogen in those cases in which an unsubstituted diepoxide is used.
- thermoset compositions of the present invention are useful in the fabrication of molded articles of manufacture, for example, by reaction injection molding techniques. If desired, the thermoset compositions can be combined with compatible reinforcing agents including glass fiber or flakes, graphite, wollastonite, mica, KEVLAR aromatic polyamide fiber, nylon fiber, and coupling agents.
- This Example illustrates the reaction of adipic acid and the diglycidyl ether of bisphenol A to form a prepolymer reactant for use in the present invention.
- This Example illustrates the formation of a poly(urethane/oxazolidone) composition from the prepolymer of Example 1.
- a 500 ml. flask was charged with 103.3 gm. of a polyol having a hydroxyl number of 378, followed by 20.9 gm. of the finely ground prepolymer from Example 1.
- the polyol composition comprised about 70%, by weight, of a 5:1 mixture of polypropylene glycol with a polyethylene glycol/ethylene glycol mixture, about 20%, by weight, of polyacrylonitrile and about 10%, by weight, of N-phenyldiethanolamine. Stirring was commenced while the mixture was heated. The temperature rose to about 60°C. in about 45 minutes, and complete solvation was achieved. The mixture was then allowed to cool, with stirring, to about 48°C. at which time the catalysts were added: 1.0 gm.
- the polymer composition was calculated to contain about 5.7 mole % oxazolidone with the remainder urethane.
- Example 2 utilizes the same general procedure shown in Example 2 for the formation of a poly-(urethane/oxazolidone) composition with the following reaction ingredients:
- the mixture from the reaction was at 72°C. when poured between two glass plates. An excellent plaque was formed and it released well.
- the polymer was calculated to contain about 11.5 mole % oxazolidone with the remainder urethane.
- This Example illustrates another synthesis of a poly(urethane/oxazolidone) composition.
- the prepolymer from Example 1 (86.4 gm.) was mixed with 63,.2 gm. of the polyol from Example 2 and heated to 70°C.. with constant mixing. When complete solvation was achieved, the mixture was allowed to cool to about 32°C. Methylene bis(4-phenyl isocyanate) was added, without any catalyst, with rapid stirring under vacuum. The mixture, after about 15 minutes, began to react. At 51°C., the mixture was poured between two glass plates. The casting was of excellent appearance and released well from between the plates. The plaque was then cured at 100°C. overnight.
- the polymer was calculated as containing about 22.9 mole% oxazolidone with the remainder urethane.
- This Example shows the synthesis of a polyurethane composition, which is not part of the present invention for testing a comparative composition against the compositions of the present invention.
- reaction mixture exothermed to 75°C. and was poured between two glass plates. The resulting plaque released well and was cured overnight at 100°C.
- This Example illustrates the synthesis of a prepolymer for use in the present invention by reacting the diglycidyl ether of bisphenol A and isophthalic acid.
- This Example illustrates preparation of a poly(oxazolidone/urethane) composition in accordance with the present invention.
- the brittle condensate from Example 6 (19.98 gm.) was ground in a blender to a size of about 840 microns and was mixed with 103.7 gm. of the polyol from Example 2. This mixture was stirred over one hour during which heating at 60°C. was applied. On cooling (33°C.), the catalysts were added: 1.0 gm. of the dibutyltin dilaurate solution from Example 2 and 0.16 gm. of ADOGEN 464 catalyst. Stirring was maintained and vacuum was applied. When the mixture became homogeneous, methylene bis(4-phenylisocyanate) was added. Vacuum was maintained, and stirring was continued. When the exothermic reaction that resulted reached 73°C., the mixture was poured between two glass plates held at 100° C. and was heated overnight (17 hours). The casting was then removed.
- the polymer was calculated as containing about 5.7 mole % oxazolidone with the remainder polyurethane.
- the prepolymer (39.9 gm.) from Example 6 was ground and stirred into 90.7 gm. of the polyol used in Example 2. Heating was applied, and the temperature of the reaction reached about 65°C. Complete solvation was achieved by stirring for about 45 min. Vacuum was applied for degassing. When the temperature fell to 33°C., the catalysts were added (0.9 gm. of the dibutyltin dilaurate solution from Example 2 and 0.31 gm. of ADOGEN 464 catalyst), and stirring was continued for about 0.5 hours. At 33°C., 112 gm of methylene bis-(4-phenylisocyanate) was added, and vacuum and stirring was maintained. When the mixture exothermed to 72°C., it was poured between two glass plates held at about 100°C. and cured at 100°C. overnight (17 hrs.). The plaque thus formed released well.
- the polymer was calculated as containing about 11.5 mole % oxazolidone with the remainder urethane.
- the prepolymer composition (79.92 gm.-) from Example 6 was ground and added to 64.7 gm. of the polyol of Example 2. The mixture was heated to 55°C. so as to dissolve the prepolymer. It was allowed to cool and vacuum was applied, with stirring, for 45 minutes. At a temperature of 33°C., 112 gm. of methylene (4-phenylisocyanate) was added '(without added catalyst) and the mixture was stirred in vacuo. The mixture was allowed to exhibit exothermicity to 50°C. at which point it was poured between two glass plates held at 100°C. The casting was released when solid (after about 42 hours) and was then cured at 100°C. overnight.
- the polymer was calculated as containing 22.9% oxazolidone with the remainder urethane.
- Example 5 illustrates the respective physical properties of the poly(oxazolidone/urethane) compositions of the present invention (Examples 2 - 4 and 7-9) as compared to a conventional polyurethane compositions (Example 5).
- the polymers of Examples 2-4 were formed from a prepolymer formed by reaction of adipic acid and the diglycidyl ether of bisphenol A (as described in Example 1);
- Examples 7-9 from a prepolymer formed by reacting isophthalic acid and the diglycidyl ether of bisphenol A (Example 6).
- This Example illustrates the formation of a prepolymer by reacting acrylic acid and the diglycidyl esther of bisphenol A followed by reaction of the prepolymer with a diisocyanate to form a poly-(urethane/oxazolidone) composition.
- Glacial acrylic acid (43.2 gm., 0.6 mole) was then added over a period of about 1.5 hours. Heating and stirring was continued for an additional 1.5 hours after the addition of acrylic acid had been completed. The mixture was cooled and allowed to remain overnight. The resulting prepolymer mixture had an acid number of 12.66 and an epoxide equivalent of 358.
- the prepolymer mixture prepared above was then reacted with methylene bis(4-phenylisocyanate).
- 30.0 gm. of the prepolymer composition was mixed with 0.25 gm. of ADOGEN 464 catalyst and degased with stirring for about one hour.
- To this mixture was then added 20.7 gm. of methylene bis (4-phenylisocyanate)to which 0.05 gm.
- VAZO 52 brand azobisisobutyronitrile catalyst
- This Example shows formation of a poly-(urethane/oxaxolidone) composition by reaction of the prepolymer of Example 11, butyl acrylate, and a diisocyanate.
- This Example illustrates formation of a poly-(urethane/oxazolidone) composition from the prepolymer of Example 11, butyl acrylate, and diisocyanate.
- the resulting mixture was stirred and heated at 67°C. for 75 min. when the temperature was raised to 90°C. for 45 min. The mixture was then cooled to 45°C. and 81.0 gm. (0.29 mole) of methylene bis (4-phenylisocyanate) was added. Stirring of the mixture was continued, and the temperature began to rise quickly. The mixture cured within the reactor. The resulting polymer was removed and cured at 100°C. overnight.
- This Example is similar to the preceding one with the exception that hydroxyethylmethacrylate is used as a reaction ingredient rather than butyl acrylate.
- This Example illustrates formation of poly(urethane/oxazolidone) compositions by reaction of the prepolymer of Example 11, butyl acrylate polymer, the diglycidyl ether of bisphenol A, butyl acrylate monomer, anddiisocyanate.
- n-butyl acrylate 39.2 gm.
- the homopolymerization of n-butyl acrylate was carried out by first purging the acrylate monomer with nitrogen for 10 minutes followed by addition of 0.02 gm. of azobisisobutyronitrile catalyst (VAZO 64 brand). After 1-1/2 hours an additional 0.02 gm. of catalyst was added, and the reaction commenced. In about 10 minutes a sticky solid mass of polybutyl acrylate was produced.
- VAZO 64 brand azobisisobutyronitrile catalyst
- the polybutyl acrylate (about 30 gm.) was stirred in vacuo with 60 gm. of the prepolymer from Example 11 and 55 gm. of the diglycidyl ether of bisphenol A. To the resulting mixture was charged 5 gm. of butyl acrylate, 0.86 gm. of ADOGEN 464 catalyst, 0.01 g m . of VAZO 64 catalyst, and 81 gm. of degased methylene bis(4-phenylisocyanate). This mixture was stirred and the temperature rose to 47°C. from 42°C. Mixing was difficult and vacuum was applied occasionally.
- the mixture was then poured between two glass plates preheated to 100°C., and the plates and reaction mixture were placed in an oven at 90°C. overnight.
- the molded plaque was hard and released well from between the plates. The plaque was brittle but did not appear as brittle as the plaque formed in Example 14.
- This Example illustrates formation of a prepolymer by reaction acetic acid and the diglycidyl ether of bisphenol A and its subsequent reaction with a diisocyanate.
- a mixture of diglycidyl ether of bisphenol A (EPON 828 brand), 559.8 gm. or 1.5 moles) and ADOGEN 464 brand catalyst (2.4 gm.) was brought to 100°C. at which time 90.0 gm. (1.5 moles) of glacial acetic acid was added over a period of 1.5 hours. Heating was maintained at 100°C. for about 4.75 hours.
- the prepolymer mixture had an acid number of 17, due to the presence of unreacted acid, and an epoxy equivalent of 401. It comprised 50% monoacetate, 25% diacetate, and 25% unreacted diepoxide.
- the prepolymer mixture thus produced (238 gm.) and 1.8 gm. of ADOGEN 464 catalyst were mixed and pumped for about one hour.
- To the resulting mixture was then added 138.7 gm. (0.5 mole) of methylene bis (4-phenylisocyanate). Mixing was continued in vacuo until the temperature reached 28°C. Mixing was difficult, however, in about 10 minutes the solution became homogenous. The temperature of the solution rose to 50°C. when it was poured between heated glass plates at about 100°C. A solid cured plaque was not obtained although chunks of solid product were isolated. These chunks were cured at 100°C. overnight, and produced somewhat brittle compositions.
- This Example is similar to the preceding Example.
- Example 16 The prepolymer formed in Example 16 (80.16 gm., epoxide equivalent: 401), the diglycidyl ether of bisphenol A (74.64 gm., 0.2 mole) and 1.3 gm. of ADOGEN 464 catalyst were stirred in vacuo for about 45 minutes. The vacuum was broken and 110.96 gm. (0.4 mole) of methylene bis (phenylisocyanate) was added. The mixture was stirred in vacuo until the temperature rose to about 30°C. from 23°C. The mixture was poured between two plates sprayed with a release agent. These plates were heated to 100°C. overnight, and the mixture between them solidified. It contained bubbles and did not release from the plates. The product was judged to be as brittle as the product from Example 16.
- This Example is similar to the preceding Example with the major exception that a polyol was also present as a reactant.
- This Example illustrates formation of thermoset compositions using the prepolymer mixture of Example 16 to prepare a composition containing 23 mole % oxazolidone.
- Example 16 (79.6 gm., epoxide equivalent 442), 162.5 gm. of the polyol from Example 2, 0.67 gm. of ADOGEN 464 catalyst, and 9.9 gm. of 0.1%, by weight, solution of dibutyltin dilaurate in the polyol from Example 2 were mixed in vacuo for about 30 min.
- l12 gm. of ISONATE 191 diisocyanate with mixing in vacuo. When the mixture exothermed to 55°C. it was poured between two glass plates held at 100°C. and was cured at 100°C. for 17 hours.
- This Example is similar in general procedure to the preceding Example.
- Example 16 39.8 gm.
- 89.5 gm. of the polyol from Example 2 89.5 gm. of the polyol from Example 2, 0.6 gm. of ADOGEN 464 catalyst, and 1.03 gm. of a 0.1% solution of dibutyltin dilaurate catalyst in the polyol from Example 2 were mixed in vacuo for about 30 minutes followed by addition of 112 gm. of ISONATE 191 diisocyanate.
- the mixture was pumped and allowed to exotherm to 62°C. At this temperature, the mixture was poured between two glass plates held at 100°C. and the mixture was cured at 100°C. for 17 hours.
- This Example is similar to the preceding Example.
- the prepolymer mixture of Example 16 (19.9 gm.), 103 gm. of the polyol from Example 2, 0.6 gm. of ADOGEN 464 catalyst, and 1.09 gm. of a 0.1% solution of dibutyltin dilaurate catalyst in the polyol from Example 2 were mixed in vacuo for about 30 minutes followed by addition of 112 gm. of ISONATE 191 diisocyanate.
- the mixture was pumped and allowed to exotherm to 72°C. At this temperature, the mixture was poured between two glass plates held at 100°C., and the mixture was cured at 100°C. for 17 hours.
- thermoset products of Examples 19-21 as follows:
Abstract
Description
- The present invention relates to compositions for the production of poly(oxazolidone/urethane) thermosets and to products prepared therefrom.
- Thermoset compositions containing oxazolidone and urethane linkages have been described in the prior art.
- U. S. Patent No. 3,242,108 to C. W. McGray, Jr. et al. describes reaction of a monomeric polyepoxide, an organic polyisocyanate, and an organic compound containing an active hydrogen atom, e.g., a carboxylic acid, in the presence of a boron trifluoride-amine complex. This patent indicates that the epoxide reactant can be prereacted to form a prepolymer. The compositions resulting from such a reaction have been characterized as resulting in the simultaneous formation of isocyanurate, oxazolidone and urethane bonds (U.S. Patent No. 4,220,731 to P. Zuppinger).
- U.S. Patent No. 3,313,747 to C. H. Schramm describes formation of isocyanate-oxazolidone derivatives by reacting a polyisocyanate with a diepoxide to yield a polyisocyanate-2-oxazolidone compound containing at least two 2-oxazolidone groups and two isocyanate groups. These compounds can be reacted with various polymerization or curing agents including polyols. Polymers resulting from reaction using a polyol curing agent would not contain ester linkages since a carboxylic acid reagent is not used in their synthesis.
- The formation of polymers containing oxazolidone and urethane linkages by reaction of polyisocyanate with a prepolymer formed by a two step reaction involving (1) reaction of a dicarboxylic acid or anhydride (e.g., phthalic anhydride) and saturated dihydric alcohol followed by (2) reaction with a diepoxide is described in U.S. Patent No. 3,847,874 to Y. Murakami et al. The reaction conditions described in this patent yield a prepolymer which contains a hydroxy group at one end and a terminal epoxide group with adjacent secondary, non-terminal hydroxy group at the other end. The diisocyanate will react with such a prepolymer to form a polymer having a recurring unit which contains urethane and oxazolidone linkages in its backbone and urethane side chains.
- U.S. Patent No. 4,066,628 to K. Ashida et al. illustrates preparation of a urethane-modified polyoxazolidone by reacting a diisocyanate and a diepoxide to form an isocyanate-terminated polyoxazolidone which is then reacted with a glycol. The resulting polymer composition contains both oxazolidone and urethane linkages in the same polymer chain or backbone of the recurring unit.
- U.S. Patent'No. 4,220,731 to P. Zuppinger relates to formation of crosslinked polymers by reacting a liquid epoxide compound, a polyisocyanate and a polyhydroxy compound, including a polyester polyol, if desired. The recurring unit would contain oxazolidone and urethane linkages in the same polymer chain.
- The present invention relates to reaction mixtures comprising a polyisocyanate and an epoxy and hydroxy-group containing prepolymer formed by reaction of a diepoxy compound with a mono- or, preferably, dicarboxylic acid. The prepolymer has an equal number of epoxy and hydroxy groups, the hydroxy group or groups being secondary and in a non-terminal position. Reaction of the polyisocyante with such a prepolymer yields a poly(oxazolidone/urethane) thermoset which is substantially free of isocyanurate linkages. The oxazolidone rings form in the polymer backbone of the recurring unit in the polymer composition due to reaction of the terminal epoxy groups with isocyanate groups, said oxazolidone groups being separated from one another by ester linkages which are derived from the acid reactant used to make the prepolymer. When a diacid is used to form the prepolymer which is reacted with the polyisocyanate, urethane groups are formed in side chains to the polymer backbone in the recurring unit due to reaction of the secondary, non-terminal hydroxy groups with the isocyanate.
- The reaction mixture which is the subject matter of the present invention comprises a polyisocyanate and a prepolymer containing equal numbers of terminal epoxy groups and secondary, non-terminal hydroxy groups. Reaction of the polyisocyanate with the epoxy group of the prepolymer forms oxazolidone groups; reaction with the non-terminal, secondary hydroxy groups, urethane side chains in the recurring unit.
- Any polyisocyanate capable of reaction with the epoxy and hydroxy groups contained in the prepolymer to form the desired oxazolidone and urethane linkages is contemplated for use by the present invention. Representative examples of suitable conventional polyisocyanates, which are used to form urethane polymers, for example, include such aromatic and aliphatic types as: the tolylene diisocyanates, such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; the methylene bis(phenyl isocyanates), such as methylene bis (4-phenyl isocyanate); dianisidine diisocyanate, toluidine diisocyanate, m-xylene diisocyanate, 1,5-naphthylene diisocyanate, p-phenylene diisocyanate, and hexamethylene diisocyanate and other di- and higher polyisocyanates. Mixtures of such isocyanates can be used, if desired.
- The prepolymer which forms the other major reaction ingredient has the formula
- When monocarboxylic acids are used, it is preferred to add the acid to a slight excess of the diepoxide so as to favor the reaction in which one side of the diepoxide reacts thereby generating a secondary non-terminal -OH group at that end while leaving the terminal epoxide group at the other end unreacted:
- Reaction of monocarboxylic acids will generally result in a statistical mixture of desired prepolymer, fully reacted epoxide reagent containing no terminal epoxy groups, and unreacted diepoxide. It should be appreciated that the prepolymer resulting from the reaction of a monoacid and the diepoxide has one terminal epoxy group and one secondary hydroxy group. The end of the prepolymer remote from the terminal epoxy group is capped with an ester linkage. Reaction of a diisocyanate, for example, with such a prepolymer produces oxazolidone and urethane linkages in the same chain of the recurring unit, i.e., the polymer backbone, with the ester groups being in pendant side chains.
- Reaction of diacids with the diepoxides is favored and is preferably carried out using slightly more than two moles of diepoxide to diacid. In this manner all the acid is reacted and a prepolymer is formed by reacting the terminal epoxy group of one epoxide reactant with one end of the diacid and the terminal epoxy group of another epoxide reactant with the other end of the diacid:
- When a diisocyanate, for example, is reacted with the prepolymer from a diacid and diepoxide, the fact that the prepolymer is capped at-both ends by epoxy groups forces formation of oxazolidone linkages in the polymer backbone of the recurring unit only. The presence of the non-terminal, secondary hydroxy groups, forces urethane formation in pendant side chains of the recurring unit.
- In both of the cases given above, the prepolymer that results, is preferably, substantially acid free and has one or two terminal epoxy groups, each with an associated, non-terminal secondary hydroxy group.
- The diepoxide and acid reactants that can be used to form the prepolymers described above can be selected from a wide variety of compounds as long as the above type of reaction occurs.
- The type of diepoxides shown in U.S. Patent No. 4,066,628 to K. Ashida et al., which is incorporated herein by reference, can be employed for use in connection with the present invention. Such diepoxides include the diglycidyl ethers of dihydric mononuclear and fused ring phenols, the diglycidyl ethers of non-fused polynuclear phenols having an alkylene, sulfone, carboxy, oxygen or sulfur bridging group between the phenol rings, the diglycidyl ethers of novolac resins, dicyclopentadiene dioxide, vinyl cyclohexane dioxide, the dicyclohexyl oxide carboxylates, and the diglycidyl derivatives of aromatic primary amines. Some representative diepoxides include the diglycidyl ethers of bisphenol A, hydroquinone, resorcinal, catechol, methylhydroquinone, 1,6-hexanediol, and 1,12-dodecanediol; alicyclic diepoxides, such as vinylcyclohexene dioxide, and dicyclopentadiene dioxide.
- The acids that can be used include the saturat- edfand unsaturated mono-and dicarboxylic acids. Representative acids include: acetic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, oxalic acid, succinic acid, acrylic acid, methacrylic acid, α-phenylacrylic acid, §=chloroacrylic acid, α-chloroacetic acid, etc.
- Once the prepolymer has been formed it is combined with the desired polyisocyanate to form a reaction mixture from which the poly(oxazolidone/ urethane) thermoset compositions can be formed, including those of the present invention which depend upon use of a diacid reactant to form the prepolymer. If desired, the reaction medium can contain up to about 60%, by weight, of other materials which do not interfere with the reaction of the prepolymer and polyisocyanate. Representative ingredients include additional diepoxide (which can function as a solvent, if liquid), diol, acrylate or methacrylate ester monomer or polymer to impart flexibility to the final product. If desired, the reaction mixture can contain up to 10%, by weight, of one or more of the following additives: blowing agents, flame retardants, mold releasing agents, dyes, and stabilizers.
- The amount of polyisocyanate chosen for reaction with the prepolymer should be substantially equivalent in regard to its isocyanate functionality (on an equivalent basis) to the total equivalents of epoxide and hydroxy groups in the composition from the prepolymer and any added ingredients which would react with the isocyanate. A slight excess of isocyanate (up to about 5% on a weight basis) can be tolerated but greater amounts should be avoided since the formation of isocyananurate linkages would be favored. In general, the respective molar amount of oxazolidone and urethane linkages to one another in the thermoset will depend upon the presence of other isocyanate reactive groups added to the reaction mixture. If only prepolymer and polyisocyanate are used a 50:50 (oxazolidone:urethane) molar ratio polymer is produced. Addition of additional hydroxy group compounds, e.g., polyol, will yield a larger molar amount of urethane, whereas addition of epoxide materials, e.g., diepoxides, will increasethe oxazolidone content of the product. The molar amount of oxazolidone to urethane can range from 90:10 to 4:96.
- In order to favor formation of oxazolidone and urethane linkages in the thermoset composition, the reaction mixture of polyisocyanate and prepolymer can also contain a catalytically effective amount (e.g., from about 0.002% to about 2%, based on the weight of all reaction ingredients of an oxazolidone and/or urethane formation catalyst. Representative catalysts tending to favor oxazolidone formation include the quarternary ammonium salts (e.g., tetramethyl ammonium chloride); the metal alkoxides (e.g., lithium n-butoxide); the metal halides and their complexes (e.g., lithium chloride/hexamethylphosphor- amide complex); and the organometallic compounds (e.g. trialkyl aluminum). Catalysts which favor urethane formation include the organotin compounds, diamines, and polyamines.
- The resulting thermoset composition formed from the above-described reaction mixture is one which contains oxazolidone and urethane linkages and which is essentially free of substantial amounts of isocyanurate linkages. The oxazolidone linkages are in the polymer backbone of the main recurring unit in virtue of their formation by reaction of.the polyisocyanate with a terminal epoxy group in the prepolymer. The urethane groups are in side chains in the main recurring unit of the polymer, rather than in the backbone of the recurring unit which contains the oxazolidone linkages, when a diacid is used to form the prepolymer described herein, in view of their formation by reaction of the polyisocyanate with the pendant, non-terminal hydroxy groups in such a prepolymer. Ester groups also lie in the polymer backbone of the unit and separate the oxazolidone groups. These ester groups are derived by reason of the reaction of a carboxylic acid with a diepoxide in forming the prepolymer.
- The main recurring unit in the thermoset compositions of the present invention, which are derived from the reaction of the prepolymer and the polyisocyanate, has the formula reproduced below which is bounded by dotted lines:
- The thermoset compositions of the present invention are useful in the fabrication of molded articles of manufacture, for example, by reaction injection molding techniques. If desired, the thermoset compositions can be combined with compatible reinforcing agents including glass fiber or flakes, graphite, wollastonite, mica, KEVLAR aromatic polyamide fiber, nylon fiber, and coupling agents.
- This Example illustrates the reaction of adipic acid and the diglycidyl ether of bisphenol A to form a prepolymer reactant for use in the present invention.
- A mixture of 248.8 gm. (0.67 mole) of the diglycidyl ether of bisphenol A, available as EPON 828 brand from Shell Chemical Co., 48.5 gm. (0.33 mole) of adipic acid, and 1.8 gm. of methyltrialkyl (C8-C10) ammonium chloride catalyst, available as ADOGEN 464 brand from Sherex Chemical Company, was heated at 100°C. over a period of about 5 hours until the acid number was 1.0±0.5. The product had an epoxy equivalent of 465.
- This Example illustrates the formation of a poly(urethane/oxazolidone) composition from the prepolymer of Example 1.
- A 500 ml. flask was charged with 103.3 gm. of a polyol having a hydroxyl number of 378, followed by 20.9 gm. of the finely ground prepolymer from Example 1. The polyol composition comprised about 70%, by weight, of a 5:1 mixture of polypropylene glycol with a polyethylene glycol/ethylene glycol mixture, about 20%, by weight, of polyacrylonitrile and about 10%, by weight, of N-phenyldiethanolamine. Stirring was commenced while the mixture was heated. The temperature rose to about 60°C. in about 45 minutes, and complete solvation was achieved. The mixture was then allowed to cool, with stirring, to about 48°C. at which time the catalysts were added: 1.0 gm. of 0.1%, by weight, solution of dibuyltin dilaurate in the above-described polyol; and 0.16 gm. of the ADOGEN 464 catalyst used in Example 1. Mixing was then contiunued under vacuum for about 15 min. and 112 gm. of methylene bis(4-phenyl-isocyanate) (ISONATE 191 brand from Upjohn Chemical Co.) was added. Stirring was maintained until the temperature reached 77°C. The resulting material was then poured between two glass plates held at 100°C. overnight.
- The polymer composition was calculated to contain about 5.7 mole % oxazolidone with the remainder urethane.
-
- The mixture from the reaction was at 72°C. when poured between two glass plates. An excellent plaque was formed and it released well.
- The polymer was calculated to contain about 11.5 mole % oxazolidone with the remainder urethane.
- This Example illustrates another synthesis of a poly(urethane/oxazolidone) composition.
- The prepolymer from Example 1 (86.4 gm.) was mixed with 63,.2 gm. of the polyol from Example 2 and heated to 70°C.. with constant mixing. When complete solvation was achieved, the mixture was allowed to cool to about 32°C. Methylene bis(4-phenyl isocyanate) was added, without any catalyst, with rapid stirring under vacuum. The mixture, after about 15 minutes, began to react. At 51°C., the mixture was poured between two glass plates. The casting was of excellent appearance and released well from between the plates. The plaque was then cured at 100°C. overnight.
- The polymer was calculated as containing about 22.9 mole% oxazolidone with the remainder urethane.
- This Example shows the synthesis of a polyurethane composition, which is not part of the present invention for testing a comparative composition against the compositions of the present invention.
-
- The reaction mixture exothermed to 75°C. and was poured between two glass plates. The resulting plaque released well and was cured overnight at 100°C.
- This Example illustrates the synthesis of a prepolymer for use in the present invention by reacting the diglycidyl ether of bisphenol A and isophthalic acid.
-
- All reactants were mixed and heated at 100°C. for about 7 hours. The reaction mixture was then poured into chloroform (about 1.66 liters). When all of the prepolymer dissolved, suspended solids were removed by filtration. The product, after evaporation of the chloroform, had an epoxy equivalent of 444.
- This Example illustrates preparation of a poly(oxazolidone/urethane) composition in accordance with the present invention.
- The brittle condensate from Example 6 (19.98 gm.) was ground in a blender to a size of about 840 microns and was mixed with 103.7 gm. of the polyol from Example 2. This mixture was stirred over one hour during which heating at 60°C. was applied. On cooling (33°C.), the catalysts were added: 1.0 gm. of the dibutyltin dilaurate solution from Example 2 and 0.16 gm. of ADOGEN 464 catalyst. Stirring was maintained and vacuum was applied. When the mixture became homogeneous, methylene bis(4-phenylisocyanate) was added. Vacuum was maintained, and stirring was continued. When the exothermic reaction that resulted reached 73°C., the mixture was poured between two glass plates held at 100° C. and was heated overnight (17 hours). The casting was then removed.
- The polymer was calculated as containing about 5.7 mole % oxazolidone with the remainder polyurethane.
- The prepolymer (39.9 gm.) from Example 6 was ground and stirred into 90.7 gm. of the polyol used in Example 2. Heating was applied, and the temperature of the reaction reached about 65°C. Complete solvation was achieved by stirring for about 45 min. Vacuum was applied for degassing. When the temperature fell to 33°C., the catalysts were added (0.9 gm. of the dibutyltin dilaurate solution from Example 2 and 0.31 gm. of ADOGEN 464 catalyst), and stirring was continued for about 0.5 hours. At 33°C., 112 gm of methylene bis-(4-phenylisocyanate) was added, and vacuum and stirring was maintained. When the mixture exothermed to 72°C., it was poured between two glass plates held at about 100°C. and cured at 100°C. overnight (17 hrs.). The plaque thus formed released well.
- The polymer was calculated as containing about 11.5 mole % oxazolidone with the remainder urethane.
- .The prepolymer composition (79.92 gm.-) from Example 6 was ground and added to 64.7 gm. of the polyol of Example 2. The mixture was heated to 55°C. so as to dissolve the prepolymer. It was allowed to cool and vacuum was applied, with stirring, for 45 minutes. At a temperature of 33°C., 112 gm. of methylene (4-phenylisocyanate) was added '(without added catalyst) and the mixture was stirred in vacuo. The mixture was allowed to exhibit exothermicity to 50°C. at which point it was poured between two glass plates held at 100°C. The casting was released when solid (after about 42 hours) and was then cured at 100°C. overnight.
- The polymer was calculated as containing 22.9% oxazolidone with the remainder urethane.
- This Example illustrates the respective physical properties of the poly(oxazolidone/urethane) compositions of the present invention (Examples 2-4 and 7-9) as compared to a conventional polyurethane compositions (Example 5). The polymers of Examples 2-4 were formed from a prepolymer formed by reaction of adipic acid and the diglycidyl ether of bisphenol A (as described in Example 1); Examples 7-9, from a prepolymer formed by reacting isophthalic acid and the diglycidyl ether of bisphenol A (Example 6).
- This Example illustrates the formation of a prepolymer by reacting acrylic acid and the diglycidyl esther of bisphenol A followed by reaction of the prepolymer with a diisocyanate to form a poly-(urethane/oxazolidone) composition.
-
- Glacial acrylic acid (43.2 gm., 0.6 mole) was then added over a period of about 1.5 hours. Heating and stirring was continued for an additional 1.5 hours after the addition of acrylic acid had been completed. The mixture was cooled and allowed to remain overnight. The resulting prepolymer mixture had an acid number of 12.66 and an epoxide equivalent of 358.
- The prepolymer mixture prepared above was then reacted with methylene bis(4-phenylisocyanate). To accomplish this reaction, 30.0 gm. of the prepolymer composition was mixed with 0.25 gm. of ADOGEN 464 catalyst and degased with stirring for about one hour. To this mixture was then added 20.7 gm. of methylene bis (4-phenylisocyanate)to which 0.05 gm.
- of azobisisobutyronitrile catalyst (VAZO 52 brand) had been added. The mixture was mixed under vacuum for about 35 minutes, poured on a glass sheet, and heated at 100°C. After 10 minutes the mixture hardened with the formation of bubbles. Heating was continued for a total of 7 hours. The resulting product was brittle, much like glass, and was not tough.
- This Example shows formation of a poly-(urethane/oxaxolidone) composition by reaction of the prepolymer of Example 11, butyl acrylate, and a diisocyanate.
- The prepolymer from Example 11 (30.0 gm., epoxide equivalent 358)and 0.25 gm. of ADOGEN 464 brand catalyst were degassed and mixed for about 20 minutes. At this point 9.54 gm. (0.0745 mole) of n-butyl acrylate was added. Degasing cound not be performed due to the high level of monomer volatiles. Methylene bis (4-phenyl-isocyanate), 20.7 gm. or 0.0746 mole, and 0.6 gm. of 2,2'-azobis(2,4-dimethylvaleronitrile catalyst (VAZO 52 brand) were then added, and the mixture was stirred with attempts made to degas it. The mixture was then poured into a PETRI dish and was heated at 100°C. for about three hours. The resulting cured disk showed many bubbles and stress cracks.
- This Example illustrates formation of a poly-(urethane/oxazolidone) composition from the prepolymer of Example 11, butyl acrylate, and diisocyanate.
-
- The resulting mixture was stirred and heated at 67°C. for 75 min. when the temperature was raised to 90°C. for 45 min. The mixture was then cooled to 45°C. and 81.0 gm. (0.29 mole) of methylene bis (4-phenylisocyanate) was added. Stirring of the mixture was continued, and the temperature began to rise quickly. The mixture cured within the reactor. The resulting polymer was removed and cured at 100°C. overnight.
- This Example is similar to the preceding one with the exception that hydroxyethylmethacrylate is used as a reaction ingredient rather than butyl acrylate.
- The prepolymer from Example 11 (60 gm., epoxide equivalent 358), hydroxyethylmethacrylate (18.9 gm., 0.15 mole) ,and 0.08 gm. of azobisisobutyronitrile catalyst (VAZO 64 brand) were mixed. The mixture was degased, blanketed with nitrogen and heated to 62°C. After 3 1/2 hours the viscosity of the reaction mixture increased 600%. At this point 55 gm. (0.15 mole) of the diglycidyl ether of bisphenol A (EPON 828) and 0.6 gm. of ADOGEN 464 brand catalyst were added. The mixture was not heated but was stirred and degassed for about 30 minutes. Then 121 gm. (0.44 mole) of methylene bis(4-phenylisocyanate) followed by stirring and degassed. The initial temperature of the mixture was 32°C. and was allowed to rise to 50°C. The mixture was then poured between two glass plates that had been preheated at 90°C. The plates and reaction mixture were heated at 90°C. overnight. The brittle, glasslike composition released well from between the plates.
- This Example illustrates formation of poly(urethane/oxazolidone) compositions by reaction of the prepolymer of Example 11, butyl acrylate polymer, the diglycidyl ether of bisphenol A, butyl acrylate monomer, anddiisocyanate.
- The homopolymerization of n-butyl acrylate (39.2 gm.) was carried out by first purging the acrylate monomer with nitrogen for 10 minutes followed by addition of 0.02 gm. of azobisisobutyronitrile catalyst (VAZO 64 brand). After 1-1/2 hours an additional 0.02 gm. of catalyst was added, and the reaction commenced. In about 10 minutes a sticky solid mass of polybutyl acrylate was produced.
- The polybutyl acrylate (about 30 gm.) was stirred in vacuo with 60 gm. of the prepolymer from Example 11 and 55 gm. of the diglycidyl ether of bisphenol A. To the resulting mixture was charged 5 gm. of butyl acrylate, 0.86 gm. of ADOGEN 464 catalyst, 0.01 gm. of VAZO 64 catalyst, and 81 gm. of degased methylene bis(4-phenylisocyanate). This mixture was stirred and the temperature rose to 47°C. from 42°C. Mixing was difficult and vacuum was applied occasionally. The mixture was then poured between two glass plates preheated to 100°C., and the plates and reaction mixture were placed in an oven at 90°C. overnight. The molded plaque was hard and released well from between the plates. The plaque was brittle but did not appear as brittle as the plaque formed in Example 14.
- This Example illustrates formation of a prepolymer by reaction acetic acid and the diglycidyl ether of bisphenol A and its subsequent reaction with a diisocyanate.
- A mixture of diglycidyl ether of bisphenol A (EPON 828 brand), 559.8 gm. or 1.5 moles) and ADOGEN 464 brand catalyst (2.4 gm.) was brought to 100°C. at which time 90.0 gm. (1.5 moles) of glacial acetic acid was added over a period of 1.5 hours. Heating was maintained at 100°C. for about 4.75 hours. The prepolymer mixture had an acid number of 17, due to the presence of unreacted acid, and an epoxy equivalent of 401. It comprised 50% monoacetate, 25% diacetate, and 25% unreacted diepoxide.
- The prepolymer mixture thus produced (238 gm.) and 1.8 gm. of ADOGEN 464 catalyst were mixed and pumped for about one hour. To the resulting mixture was then added 138.7 gm. (0.5 mole) of methylene bis (4-phenylisocyanate). Mixing was continued in vacuo until the temperature reached 28°C. Mixing was difficult, however, in about 10 minutes the solution became homogenous. The temperature of the solution rose to 50°C. when it was poured between heated glass plates at about 100°C. A solid cured plaque was not obtained although chunks of solid product were isolated. These chunks were cured at 100°C. overnight, and produced somewhat brittle compositions.
- This Example is similar to the preceding Example.
- The prepolymer formed in Example 16 (80.16 gm., epoxide equivalent: 401), the diglycidyl ether of bisphenol A (74.64 gm., 0.2 mole) and 1.3 gm. of ADOGEN 464 catalyst were stirred in vacuo for about 45 minutes. The vacuum was broken and 110.96 gm. (0.4 mole) of methylene bis (phenylisocyanate) was added. The mixture was stirred in vacuo until the temperature rose to about 30°C. from 23°C. The mixture was poured between two plates sprayed with a release agent. These plates were heated to 100°C. overnight, and the mixture between them solidified. It contained bubbles and did not release from the plates. The product was judged to be as brittle as the product from Example 16.
- This Example is similar to the preceding Example with the major exception that a polyol was also present as a reactant.
- The prepolymer from Example 16 (72.1 gm., epoxide, equivalent: 401), the polyol from Example 2 having a hydroxyl number of 378 (63.2 gm., 0.46 mole), and 0.88 gm. of ADOGEN 464 catalyst were mixed in vacuo for about 45 minutes. The methylene bis(4-phenylisocyanate), 109.0 gm. or 0.393 mole, was then added, and stirring and application of vacuum was resumed. The reaction temperature rose to 50°C. when the mixture was poured between two glass plates preheated at 100°C. The plates containing the product was heated at 100°C. overnight. The cured product released from the plates and contained bubbles. It was brittle and tougher than the product from Example 17.
- This Example illustrates formation of thermoset compositions using the prepolymer mixture of Example 16 to prepare a composition containing 23 mole % oxazolidone.
- The prepolymer mixture of Example 16 (79.6 gm., epoxide equivalent 442), 162.5 gm. of the polyol from Example 2, 0.67 gm. of ADOGEN 464 catalyst, and 9.9 gm. of 0.1%, by weight, solution of dibutyltin dilaurate in the polyol from Example 2 were mixed in vacuo for about 30 min. To this mixture was added l12 gm. of ISONATE 191 diisocyanate with mixing in vacuo. When the mixture exothermed to 55°C. it was poured between two glass plates held at 100°C. and was cured at 100°C. for 17 hours.
- The physical properties of this material are given in Example 22.
- This Example is similar in general procedure to the preceding Example.
- The prepolymer mixture of Example 16 (39.8 gm.), 89.5 gm. of the polyol from Example 2, 0.6 gm. of ADOGEN 464 catalyst, and 1.03 gm. of a 0.1% solution of dibutyltin dilaurate catalyst in the polyol from Example 2 were mixed in vacuo for about 30 minutes followed by addition of 112 gm. of ISONATE 191 diisocyanate. The mixture was pumped and allowed to exotherm to 62°C. At this temperature, the mixture was poured between two glass plates held at 100°C. and the mixture was cured at 100°C. for 17 hours.
- The physical properties of this material are given in Example 22.
- This Example is similar to the preceding Example. To prepare a composition containing 6 mole % oxazolidone, the prepolymer mixture of Example 16 (19.9 gm.), 103 gm. of the polyol from Example 2, 0.6 gm. of ADOGEN 464 catalyst, and 1.09 gm. of a 0.1% solution of dibutyltin dilaurate catalyst in the polyol from Example 2 were mixed in vacuo for about 30 minutes followed by addition of 112 gm. of ISONATE 191 diisocyanate. The mixture was pumped and allowed to exotherm to 72°C. At this temperature, the mixture was poured between two glass plates held at 100°C., and the mixture was cured at 100°C. for 17 hours.
- The physical properties of this material are given in Example 22.
-
- These data illustrate that as the oxazolidone content of the composition increased, the tensile strength at yield.and break, the percent elongation at
- yield, the elastic modulus, and the tangent modulus of elasticity increase while the percent elongation at break, tensile impact and Izod impact decrease.
-
- As shown in Table I, as the oxazolidone content of the polymer mixture increases, less material is lost due to thermal degradation.
Claims (15)
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US309732 | 1981-10-08 | ||
US06/309,732 US4424316A (en) | 1981-10-08 | 1981-10-08 | Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom |
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BR (1) | BR8205890A (en) |
CA (1) | CA1210889A (en) |
CS (1) | CS236490B2 (en) |
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EP0127976A2 (en) * | 1983-06-01 | 1984-12-12 | Stauffer Chemical Company | Modified poly(oxazolidone/urethane) compositions |
EP0850964A1 (en) * | 1996-12-23 | 1998-07-01 | Basf Aktiengesellschaft | Oxazolidone- and urethane groups containing, isocyanate-terminated prepolymers, being under pressure, for one-component foams |
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CA1340052C (en) * | 1988-03-31 | 1998-09-22 | Narasimhan Raghupathi | Chemically treated glass fibers for reinforcing thermosetting polymer matrices |
EP0342064B1 (en) * | 1988-05-13 | 1995-02-15 | Nippon Paint Co., Ltd. | A thermosetting resinous composition and preparation of heat resisting coating and molded product using said composition |
US4981754A (en) * | 1988-06-20 | 1991-01-01 | Owens-Corning Fiberglas Corporation | Glass fibers having a size composition containing the reaction product of an acid and/or alcohol with the terminal epoxy groups of a diglycidyl ether of a bisphenol |
JPH03255122A (en) * | 1990-03-02 | 1991-11-14 | Nippon Paint Co Ltd | Thermosetting resin composition and thermosetting resin molding |
US5138016A (en) * | 1990-12-18 | 1992-08-11 | H. B. Fuller Company | Isocyanurate-free oxazolidone compound made from epoxy and a hindered isocyanate compound and a novel catalyst for their production |
US5304612A (en) * | 1990-12-25 | 1994-04-19 | Teijin Limited | Plural liquid pack type heat curable polyisocyanate-glycidyl acrylate compound resinous composition and process for producing shaped resin article therefrom |
US5480958A (en) | 1994-09-21 | 1996-01-02 | Air Products And Chemicals, Inc. | Polyepoxide resins incorporating epoxy terminated urethanes as tougheners |
US7267288B2 (en) * | 2001-03-22 | 2007-09-11 | Nevada Supply Corporation | Polyurethane in intimate contact with fibrous material |
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US3847874A (en) * | 1970-01-22 | 1974-11-12 | Dainippon Ink & Chemicals | Polyurethane composition based on epoxide-modified linear polyester |
DE2545106A1 (en) * | 1974-10-11 | 1976-04-15 | Hitachi Ltd | WARM-DURABLE RESIN COMPOSITION |
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1981
- 1981-10-08 US US06/309,732 patent/US4424316A/en not_active Expired - Fee Related
-
1982
- 1982-10-06 DE DE8282305313T patent/DE3275298D1/en not_active Expired
- 1982-10-06 DD DD82243838A patent/DD203055A5/en unknown
- 1982-10-06 EP EP82305313A patent/EP0077175B1/en not_active Expired
- 1982-10-07 ES ES516312A patent/ES8403954A1/en not_active Expired
- 1982-10-07 KR KR8204516A patent/KR890003002B1/en active
- 1982-10-07 BR BR8205890A patent/BR8205890A/en unknown
- 1982-10-07 CA CA000413010A patent/CA1210889A/en not_active Expired
- 1982-10-08 JP JP57176466A patent/JPS5871914A/en active Pending
- 1982-10-08 CS CS827209A patent/CS236490B2/en unknown
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0127976A2 (en) * | 1983-06-01 | 1984-12-12 | Stauffer Chemical Company | Modified poly(oxazolidone/urethane) compositions |
EP0127976A3 (en) * | 1983-06-01 | 1986-05-07 | Stauffer Chemical Company | Modified poly(oxazolidone/urethane) compositions |
EP0850964A1 (en) * | 1996-12-23 | 1998-07-01 | Basf Aktiengesellschaft | Oxazolidone- and urethane groups containing, isocyanate-terminated prepolymers, being under pressure, for one-component foams |
US7809663B1 (en) | 2006-05-22 | 2010-10-05 | Convergys Cmg Utah, Inc. | System and method for supporting the utilization of machine language |
US8379830B1 (en) | 2006-05-22 | 2013-02-19 | Convergys Customer Management Delaware Llc | System and method for automated customer service with contingent live interaction |
US9549065B1 (en) | 2006-05-22 | 2017-01-17 | Convergys Customer Management Delaware Llc | System and method for automated customer service with contingent live interaction |
Also Published As
Publication number | Publication date |
---|---|
EP0077175A3 (en) | 1983-08-24 |
CA1210889A (en) | 1986-09-02 |
JPS5871914A (en) | 1983-04-28 |
ES516312A0 (en) | 1984-04-01 |
DE3275298D1 (en) | 1987-03-05 |
CS236490B2 (en) | 1985-05-15 |
EP0077175B1 (en) | 1987-01-28 |
DD203055A5 (en) | 1983-10-12 |
US4424316A (en) | 1984-01-03 |
KR890003002B1 (en) | 1989-08-18 |
ES8403954A1 (en) | 1984-04-01 |
BR8205890A (en) | 1983-09-06 |
KR840002010A (en) | 1984-06-11 |
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